Aqueous explosive composition containing as a sensitizer a condensation product of ethylene oxide with a phenol or saturated carboxylic acid



Int-2,

United States Patent 3,510,370 AQUEOUS EXPLOSIVE COMPOSITION CONTAIN- IN G AS A SENSITIZER A CONDENSATION PROD- UCT OF ETHYLENE OXIDE WITH A PHENOL OR SATURATED CARBOXYLIC ACID Norman McLeod Jardine, Highett, Victoria, and Gwyn Harries, Ripponlea, Victoria, Australia, assignors t-o Imperial Chemical Industries of Australia and New Zealand Limited, Melbourne, Victoria, Australia, a corporation of Australia No Drawing. Filed May 5, 1969, Ser. No. 821,950 Claims priority, application Australia, May 13, 1968, 37,702/ 68 Int. Cl. C06b 11/00 US. Cl. 149-46 7 Claims ABSTRACT OF THE DISCLOSURE This invention relates to new compositions of matter and in particular it relates to new explosive compositions of matter containing an inorganic oxidizer salt, a fuel, water, and as a sensitizer the condensation product of an alkylene oxide with a phenol or saturated carboxylic acid.

Explosive compositions in the form of slurries and comprising inorganic oxidising salts, fuel oils and water, optionally together with metals and conventional thickeners, cross-linking promoters and cross-linking retardants are known. In copending Australian patent application No. 21,822/ 67 we have already disclosed improved explosive compositions comprising an oxygen releasing inorganic salt which are explosive even in the absence of fuel oil when a water insoluble cellular material is added.

We have now found that the sensitivity of explosive slurries based on oxygen releasing inorganic salts in the absence of fuel oils may also be enhanced by certain sensitizing additives. Furthermore we have found that addition of these sensitising additives reduces variation in the sensitivity of the slurry both immediately after mixing and on prolonged storage.

Accordingly we provide explosive slurries comprising firstly, at least one oxygen releasing salt selected from the group consisting of inorganic nitrates, chlorates and perchlorates and mixtures thereof; secondly, at least one fuel; thirdly, water; and fourthly, as a sensitising additive at least one condensation product of 8 to 30 inclusive moles of a lower alkylene oxide with a compound selected from the group consisting of octyl phenols, nonyl phenols, tributyl phenols and saturated carboxylic acids having more than 8 carbon atoms, preferably more than 12 carbon atoms and not more than 24 carbon atoms in the chain.

Long chain carboxylic acids which may be reacted with the alkylene oxide are the saturated carboxylic acids having more than 8 carbon atoms and preferably more than 12 carbon atoms in the chain. Thus, for example, caprylic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, arachidic acid or mixtures thereof may be used.

By lower alkylene oxide we mean ethylene oxide or mixtures of ethylene oxide with one or more other alkylene oxides having up to 5, preferably 3 carbon atoms. Preferably the molar ratio of ethylene oxide to higher alkylene oxides, when the latter are present in the polyoxyalkylene residue of our sensitising additives, is less than 2:1 when there are 12 or fewer molecules of ethylene oxide in the said residue and less than 0.8:1 when there are more than 12 molecules of ethylene oxide in the said residue.

3 ,5 l 0,3 Patented May 5, 1970 Useful molar ratios of ethylene oxide to alkylene-oxidereactive compound range from 8:1 to 30:1 inclusive; preferred ratios range from 12:1 to 25 :1. At ratios greater than 30:1 little further benefit is achieved. In addition, as stated above, higher alkylene oxides may be present in the polyoxyalkylene residue of our agents.

Our sensitising additives are exemplified typically by the condensates set out in Table I.

TABLE I Alkylene oxide Number of moles per mole of alkylene- Sensitising Alkylene-oxideoxide-reactive Additive No. reactive compound compound Type 1 Octyl phenol 8. 5 Ethylene oxide.

2 do 10 Do.

3 do 13 Do.

Nonyl phenol 12 Do.

o 15 Do.

Mixture of octyl and 9 Do.

nonyl phenols.

9 Tributyl phenol 8 Do.

10 Octyl phenol 22 Mixture of ethylene oxide and propylene oxide.

11 Nonyl phenol 28 Mixture of ethylene oxide and butylene oxide.

12 Laurie acid 13 Ethylene oxide.

13 o 22 Do.

Coconut iattya 15 Do. 10 Do. 15 Do. 12 Mixture of ethylene and propylene 12 oxgles.

i3 14 Do.

20 Coconut fatty acid. 10 Ethylene oxide.

21 Tributyl phenol 13 Do.

22 do 18 Do.

The amount of the condensates used varies with the condensate used and the composition to which it is added. Amounts from 0.1 to 5% w./w. of the total composition are useful; we prefer that the amount be in the range from 0.2 to 2% w./w. of the total composition.

We prefer that the oxygen releasing salts be chosen from the nitrates of the alkali metals or ammonium and of these we prefer sodium nitrate and ammonium nitrate. The amount of oxygen releasing salt in our compositions is not narrowly critical; we have found that compositions containing amounts of oxygen releasing salts from 50% w./w. to 90% w./w. of the total composition are satisfactory and amounts from 65% w./w. to w./w. are preferred. The particle size and shape of the oxygen releasing salt is not critical and is well known from the art of ammonium nitrate manufacture; powders and prilled particles are satisfactory.

The nature of the fuels in our composition is determined by the requirements that they burn in the presence of oxygen or an oxygen containing gas and that their physical nature is such that they may be incorporated in our compositions in a manner so as to be substantially uniformly distributed throughout the compositions. Such fuels are well known in the art and they may be organic or inorganic and may also be derived from animals and plants.

The fuels employed in the compositions of this invention can be, for example, self-explosive fuels, non-explosive carbonaceous, non-metallic and metallic fuels or mixtures of the aforementioned types of fuels. They can be varied widely, provided that in the composition in which any particular fuel is used, the fuel is stable, that is prior to detonation, during preparation and storage the fuel is chemically inert to the system. Examples of self- 3 explosive fuels include one or more organic nitrates, nitro compounds and nitramines such as trinitrotoluene, cyclotri(or tetra)methylenetri(r tetra)nitramine, tetryl, pentaerythritol tetranitrate, explosive grade nitrocellulose and nitrostarch.

The self-explosive fuel can be for example in any of the well known flake, crystalline or pelleted forms. In general up to 35% and preferably from 10 to 30% by weight based on the weight of composition of self-explosive fuel is used.

Suitable water soluble fuels are organic water soluble substances for example urea, carbohydrates such as sugars or molasses, water soluble alcohols, glues or mixtures of these. The proportion of water soluble fuel in our compositions should be at least 0.8% w./w. and may be as high as 8% w./w. of the total composition. Amounts from 4% w./w. to 7% w./w. of the total composition are preferred.

Suitable water insoluble or sparingly water soluble fuels may be chosen from inorganic materials for example sulphur, aluminum, silicon, magnesium, titanium, boron, mixtures thereof and mixtures of aluminum with ferrosilicon, or organic materials for example finely divided charcoal, anthracite, asphalt, cellulosic materials such as sawdust, or cereal products for example flours, dextrins or starches. When the inorganic fuel is a metal it is preferably in powder form ranging in particle size from very fine, for example a powder passing a 200 8.5.5. sieve, to coarse, for example a powder retained on a 30 3.8.8. sieve. The proportion of water insoluble or sparingly 'water soluble non-metallic fuels in our composition should be in the range from 1% w./w. to 10% w./w. of the total composition and amounts from 4% w./w. to 7% w./w. of the total composition are preferred. The proportion of metallic water insoluble fuels when present in our compositions may be as high as 25% w./W. and amounts in the range from w./w. to 20% w./w. of the total compositions are preferred.

The proportion of water in our compositions should be sufiicient to dissolve at least part of the water soluble fuel when present, and part of the oxygen releasing inorganic salt say from 5% w./w. up to 35% w./w. but not be in excess of the explosive limit of the composition. We prefer that the water he in the range from 5% W./w. to 2.5% w./w. of the total composition and more preferably in the range from 12% w./w. to 17% w./w. of the total composition.

Where desirable, it is convenient to add to the compositions according to our invention, in amounts expressed as parts by weight per 100 parts by weight of the final mixture, conventional thickeners, for example, guar gum, in amounts in the range from e.g. 0 to 1 part; conventional cross-linking promoters, for example zinc chromate, in amounts in the range e.g. from 0. to 0.5 part; conventional cross-linking retardants, for example tartaric acid, in amounts ranging e.g. from 0 to 0.1 part or conventional anti-foaming agents, for example ethyl hexanol, in amounts ranging e.g. from 0 to 0.1 part.

The compositions according to this invention are usually pourable and pumpable slurries or dispersions but may also be prepared as mouldable or extrudable plastic masses. They are advantageous in that they have increased sensitivity over similar explosive compositions not containing our additives. Our additives permit blasting in smaller holes down to a diameter of 1" or less, maintain sensitivity more nearly constant than is possible with prior art compositions and consequently extend the safe period of storage. The increased sensitivity of our compositions also permits savings resulting from the reduction of the amount of detonating material required.

Our invention is now illustrated by but not limited to the following examples in which parts and percentages are expressed on a weight basis.

EXAMPLES 1 to 35 INCLUSIVE Using a mixer of the Schraeder type having a capacity of 20 lb. a blasting explosive was prepared by mixing the substances set out in Table II in proportions set out in Table II. Details of the detonation conditions are also set out in Table II. Examples 1, 5, 7, 9, 12, 14, 16, 18, 20, 22, 24, 26, 28 and 30 are not within our invention and are included for purposes of comparison.

TAB LE II Example No 1 2 3 Component Ingredient Parts of Ingredient sensitizing Additive... N0. in Table I No. 5 No. 6 0. 5 0. 5

Oxygen releasing salt:

(1) Ammonium nitrate 68. 4 68. 4 68. 4

prilled. Ammonium nitrate coarse. (2) Ammonium nitrate fine. (3) Sodium nitrate 2. 5 2. 5 2. 5

Fuel:

(4) Molasses Sugar 5.0 5. 0 5.0 Sulphur (5) Aluminium powder- 9. 0 9. 0 9. O (6) Aluminium powder fine. Urea (7) Silicon l. 0 1. 0 1. 0 Wheat flour Water Water 13.0 13.0 13. 0

Optional additives Guar gum Zinc chromate 'Iartaric acid 2 ethyl hexanol Diameter of cardboard cylinder holding charge (in.).

Minimum Pentolite required to detonate (a). Diameter of steel pipe holding charge (in.). Minimum Pentolite required to detonate Minimum number of No. 8 Al detonators required to detonate using a 4 diameter charge.

Example N0 4 5 6 Parts of Ingredient Component Ingredient sensitizing Additive.-- No. in Table I xygen releasing salt:

(1) Ammonium nitrate prilled. A mmonium nitrate coarse. (2) Ammonium nitrate ne. (3) Sodium nitrate Fuel:

(4) Molasses 5. 0 5. 9 6. 2

required to detonate Diameter of steel pipe 3 2 holding charge (in.)

Minimum Pentolite required to detonate Minimum number of N o. 8 Al detonators required to detonate using a 4 diameter charge.

Example No. 7 8 9 Example N0. 14 16 17 Component Ingredient Parts of Ingredient Component Ingredient Parts of Ingredient Sensitizing Additive- No. in Table I N o. 3 No. 3

1.3 0.5 5 sensitizing Additive No. in Table I No. 5 No. 5 0.7 0.5

Oxygen releasing salt: 7

(1) Ammonium nitrate 68. 0 69. 6 Oxygen releasing salt;

prllled. (l) Ammonium nitrate Ammonium nitrate prilled.

coarse. 1o Ammonium nitrate 53. 1 52. 6 (2) Ammonlum nitrate 71. 2 69. 0 coarse.

fine. (2) Ammonium nitrate 82. 0 81. 5 (3) Sodium nitrate 3. 0 3. 0 2. 0 fine.

(3) Sodium nitrate 5. 0 5. 0 3. 0 3. 0 Fuel:

(4) Molasses 6. 8 6. 8 Fuel:

Sugar 15 (4) Molasses 8. 0 8. 0 Sulphur 7. 0 5. 0 Sugar 8.0 (5) Aluminium powder- 10.0 9.7 8.0 10.0 Sulphur (6) Aluminium powder (5) Aluminium powder- 15. 0 15. 0 fine, (6) Aluminium powder Urea fine. (7) Silicon. Urea Wheat flour (7) Silicon Wheat flour Water Water 8. 4 10. 0 14. 0 14. 0

Water Water 18.0 18. 0 6.3 6. 3

Optional additives- Guar gum 0. 3 v

Zinc chromate 0. 2 Optional additives Guar gum 0. 8 0. 5 0. 2 Tartaric acid 0. 01 Z nc ohrom 0. 1 0. 2 O. 5 2 ethyl hexanol 0. 06 Tartarie acid 0. 01 0. 02 0. 03 2 ethyl hexan 0. 03 0. 02

Diameter of card- 4 4 4 3 board cylinder Diam ter of card- 5 5 4 4 holding charge (in.). board y nde Minimum Pentolite 150 50 150 150 holding charge (in.).

required to detonate Minimum Pentohte 250 150 10 required to detonate Diameter of steel 2 1% g.

pipe holding Dlitmeter ee charge (in.). t n holding Minimum Pentolite 150 40 charge (111.).

required to Minimum Pentohte detonate (g.). required to Minimum number of detonate (g.).

No. 8 Al detonators Mm m m num r f required to detonate N 0. 8 A detonators using a 4' diameter required to detonate charge, using a 4" diameter charge. Example No 11 12 13 N Component Ingredient Parts of Ingredient Example 0 18 19 2o 21 Component Ingredient Parts of Ingredient sensitizing Additive No. in Table I No. 3 No. 4

0. 5 1. 0 Sensltmng Add1t1ve.- No. in Table I No. 5 No. 5 0.5 0. 5

oxygen releasing Salt: Oxygen releasing salt:

( g mtrate 69. 1 (1) Ammorcllium nitrate e7. 4 as. s

r1 e Ammonium nitrate 71. 2 69- 2 gfi it t coarse. coarse g mtrate (2) Ailmonium nitrate 46. 2 4e. 2

ne. (3) Sodmm nitrate 0 0 (a) Sodium nitrate 19. 2 19. o 2. o 2, 0

Fuel: Fuel;

(4) Molasses 6. 8 6. 8 (4) M la Sugar. Sulphur (5) Aluminum powder 18.0 18.0 8. 0 8. 0 A u m powder (6) Aluminum powder 2. 0 2. 0

fine. fine. Urea Urea (7) Silicon 5. 0 5. 0 (7) sili Wheel; 0 Wheat flour. 7. 0 7. 0

Water Wa er 14. 5 4 4 Water Water 13. 0 13. 0 15, 0 15, 0

Optional additives Guar gum o. s o. a 0. 3 Optional es. ea gum 0. 6 0. 6 0.5 0.5 Zinc chromate- 0.1 0.2 0. 2 Zmc h m 1 0. 'Tartaric acid 0 01 0, 0 Tartaric ae1d 0. 01 0. 01 0. 01 2 ethyl hexanol 0 0e 0. 0e 2 ethyl hexane! Diameter of cardboard 4 5 4 Dlametel f cardcylinder holding beard y e charge (in hq m charge 5 5 Mlnimum Pentolite 150 150 150 Mmlmym Pentvllte required to detonate reqmmd to onate (g.) 150 100 Diameter of steel pipe 13133119179! Steel holding charge (in.). R 1 holding charge Minimum Pentolite required to detonate Mmlmnm Pentolltfl (g.) required to det- Mlnimum number of 0119459 N 0 8 Al detonators lmum number of required to detonate A1 detonators using a 4" diameter requlmd to chamm onate using a 4" diameter charge 6 4 Example No 22 23 24 25 Example N 32 33 34 Component. Ingredient Parts of Ingredient Component Ingredient Parts of Ingredient sensitizing Additive" No. in Table I No. 18 No. sensitizing additive... No. in Table L No.9 No. 21 No. 22 0.5 3.0 5 0.4 0.4 0.5 O: n eleasin Oxygen releasing salt:

r g (l) Ammonium nitrate 68. 4 68. 4 68. 4 (1) Ammonium nitrate 68. 4 67. 5 70. 4 67. 4 prilled.

prilled. Ammonium nitrate Ammonium nitrate c0arse.

coarse. (2). Ammonium nitrate (2) Ammonium nitrate 1O fine.

fine. (3) Sodium nitrate 2. 5 2. 5 2. 5 (3) Sodium nitrate 2. 0 2. 0 2. 5 2. 5

Fuel:

4 Fuel:

(4) Molasses Sagan-.. p sulphur (5) Alum n um powder- 9. 0 9. 0 9. 0 (5) Aluminium powder. 10.0 10. 0 9. 0 9. 0 (6) g powder (6) Aluminium powder U96? 5. 0 5. 0 Sui); Silicon V Wheat flou Water Water O tional additives. Guar gum Water Water 14. 0 14. 0 14. 0 14. 0 P Zinc chromate 1 0 1 0' 1 Tartaric acid 0. 01 0. O1 0. 01 Optional additives. Guar gum 0. 5 0.5 0.5 0.5 2 ethyl hexanol Zinc chromate 0. 1 O. 1 O. l 0. 1 'lartaric acid 0. 01 0. 0i 0. 01 o. 01 Diameter of cardboard 5 5 4 2 ethyl hexanol H cy in r holding charge (in.). Minimum Pentolite 150 150 150 Diameter of card- 5 5 5 3 required to detonate board cylinder ho ding a g Diameter of steel pipe Minimum PeIltOlllZB 2 2 1 1 holding charge (in,)

required to detonate Minimum Pentolite (g-) required to detonate Diameter of steel pipe g holding cha g Minimum number of Minimum Pentolite N0, 8 Al detonators required to detonate required to detonate using a 4 diameter Minimum NO. 0f N0. charge.

8 Al detonators required to detonate 113mg #14 dlameter Notes on Table II charge.

(1) The prilled ammonium nitrate used in Examples 1 Example N0 28 29 31 to 6 inclusive, 9 to 11 inclusive and 32 to 34 inclusive d1 was coated with a small amount of china clay. Cmnponent Ingredlent Parts of Ingre em (2) The fine ammonium nitrate was in the form of a owder 100% passing a No. 6 B 5.8 sieve 51% passing s nsitizin additive. No.1n Table I No. 3 No. 3 P 3 i e g 0.1 0.1 a No. 36 B.S.S. sieve and 18% passing a No. 100 B.S.S.

sieve. Oxyggn releasing salt: Allilllloeltllillm nitrate 70.4 70. 4 53. O 53. O (3) Th di i t was i th f f a coarse Ammonium nitrate P Acoarse. t t (4) The molasses contained 20% w./w. of water. (2) 531 m m e (5) The aluminium powder passed a No. 25 B.S.S. Sodium nitrate 0 0 0 5 sieve, not less than 70% was retained on a No. 100 B.S.S. sieve and not less than 95% was retained on a No. 300

Fuel:

(6) Aluminium powder fine.

Urea

(7) Silicon. 5. 0

Wheat flour Water Water 17. 0 17. 0 85. 0 35. 0

Optional additives. Guar gum 0. 6 0. 6 1. 0 1. 0

Zinc chromate Tartario acid" 2 ethyl hexanol For comparative purposes a composition according to Example 1 was prepared except that the coated prills of that example were replaced by an identical amount of uncoated prills of ammonium nitrate. A portion of this composition was cartridgcd in 4 diameter cardboard cylinders. The minimum amount of pentolite required to detonate a cartridge so prepared was 250 g. Another portion of this composition was pumped through a Mono pump prior to cartridging in cardboard cylinders. (Mono is a registered trademark. This pump is of the positive displacement type fitted with a screw feed). Using 250 g. of pentolite as a detonating material no detonation of the pumped composition could be obtained in a cardboard cartridge of 4 diameter, nor even in a cardboard cartridge of 5" diameter, i.e. under less stringent conditions. This example demonstrates that this comparative composition is less sensitive to detonation after pumpmg.

9 EXAMPLE 27 A composition according to Example 2 was prepared except that the coated prills of that example were replaced by an identical amount of uncoated prills of ammonium nitrate. Equal amounts of this composition were cartridged in four 4 diameter cardboard cylinders each both before and after pumping through a Mono pump. All cartridges so obtained were successfully detonated using 100 g. of pentolite.

This example demonstrates that compositions according to our invention have enhanced sensitivity both before and after pumping when compared with the compositions of Example 26.

EXAMPLE 35 The composition of Example 29 was stored for 2 days at ambient temperature. After this time it was detonated successfully under the conditions shown in Table II in Example 29. By contrast the composition of Example 28not according to our inventionunder the same storage conditions, could not be detonated under the conditions shown in Table II in Example 28. This example demonstrates that the addition of the sensitizing additive reduced the variation in the sensitivity of the slurry on prolonged storage.

We claim:

1. A composition of matter consisting essentially of (1) at least one oxygen releasing inorganic salt selected from the group consisting of ammonium nitrate, chlorate and perchlorate and alkali metal nitrates, chlorates and perchlorates present in an amount from 50 parts to 90 parts; (2) at least one fuel selected from the group consisting of water soluble fuel present in an amount from 0.8 to 8 parts, non metallic sparingly Water soluble and non metallic water insoluble fuel present in an amount from 1 to parts and metallic water insoluble fuel present in an amount from 5 to parts; (3) water present in an amount from 5 to 35 parts and (4) as a sensitising additive at least one condensation product of 8 to 30 inclusive moles of a lower alkylene oxide selected from the group consisting of ethylene oxide and mixtures of ethylene oxide and propylene oxide with a compound selected from the group consisting of octyl phenols, nonyl phenols, tributyl phenols and saturated carboxylic acids having more than 8 carbon atoms and not more than 24 carbon atoms in the chain present in an amount from 0.1 part to 5 parts, all amounts being in parts by weight per 100 parts by weight of the composition.

2. A composition of matter according to claim 1 wherein the oxygen releasing salt is selected from the group consisting of the nitrates of sodium and ammonium.

3. A composition of matter according to claim 1 wherein the oxygen releasing salt constitutes from W./w. to W./w. of the total composition.

4. A composition of matter according to claim 1 wherein fuel is selected from the group of (a) water soluble fuel, (b) non-metallic sparingly water soluble fuel and (c) non metallic water insoluble fuel or mixtures thereof and wherein any one of said fuels (a), (b) or (c) is present in amount from 4% w./w. to 7% w./w. of the total composition.

5. A composition of matter according to claim 1 wherein water constitutes from 12% w./w. to 17% w./W. of the total composition.

6. A composition of matter according to claim 1 wherein the sensitising additive condensation product contains from 12 to 25 inclusive moles of a lower alkylene oxide.

7. A composition of matter according to claim 1 wherein the sensitising additive constitutes from 0.2% W./w. to 2.0% w./w. of the total composition.

References Cited UNITED STATES PATENTS 3,390,029 6/1968 Preckel l4944X CARL D. QUARFORTH, Primary Examiner S. J. LECHERT, Assistant Examiner US. Cl. X.R. 

